Organic electroluminescence device

ABSTRACT

An organic electroluminescent (EL) device which contains a novel coumarin derivative composed of a coumarin ring, a naphthalene ring with one or more hydrocarbon groups, and a five-membered hetero ring condensed with the naphthalene ring so as to give an electronic resonance through the coumarin and naphthalene rings. The coumarin derivative emits a visible luminescence with a satisfactory color purity, which consistently continues over a long period of time even at an elevated temperature when used in such an organic device.

TECHNICAL FIELD

This invention relates to an organic electroluminescent device (abbreviated as “organic EL device” hereinafter), more particularly, to an organic EL device using a novel coumarin derivative.

BACKGROUND ART

In the field of information display, organic EL devices have been highlighted as displaying devices of the forthcoming generation. Hitherto, cathode-ray tubes have been predominantly used in information displaying equipments of larger sizes such as computer termini and TV receivers: However, cathode-ray tubes are large in volume and weight and high in operation voltage, and these may restrict their application in equipments which are directed to use at home, as well as in compact equipments where portability is one of important factors. More required are information displaying equipments which are in a thinner and lighter panel form and operable with a lower voltage and less power consumption. Liquid crystal devices have been frequently used in various fields because of the merit that they are operable with a low voltage and less power consumption. Liquid crystal devices however have the demerits that one hardly receives a clear information therefrom when he or she views them at an angle outside the specific ranges, as well as that their power consumption is not so small as expected because they usually require backlight. Organic EL device has appeared as information displaying means which may overcome these demerits.

Organic EL device is a class of light-emitting device which utilizes electroluminescence such as fluorescence or phosphorescence: It usually comprises a luminescent layer incorporated with a luminescent compound and inserted between a cathode and anode to which dc voltage is energized to inject holes and electrons in the luminescent layer so that a pair of hole and electron recouple each other to make in the luminescent compound an excited state which subsequently returns to the ground state to emit such luminescence. Organic EL device is characterized in that its luminescent color tint can be controlled to a desired level by selecting an appropriate organic compound to be used as host compound in the formation of luminescent layer, and screening guest compounds (or dopants) which may match with the host compound. There is the possibility of remarkably increasing the brightness and life expectancy for luminescence in organic EL device, dependently upon the combination of host and guest compounds. Organic EL device has been deemed to be in principle an excellent device because of the merit that it does realize an autonomous light emission and this would advantageously save power consumption.

Many of organic EL devices proposed hitherto however have the problem that they are low in durability, and therefor their brightness decreases within a short period of time when used under severe conditions, for example, in case of equipping them to automobiles where mechanical vibrations and high temperatures are unavoidable.

In view of such situation, the objectives of this invention are to provide a luminescent agent which would be useful even in highly durable organic EL devices, as well as to provide its uses.

DISCLOSURE OF INVENTION

To attain these objectives, the present inventors eagerly researched and screened coumarin derivatives, resulting in the finding that in organic EL devices, a coumarin derivative which comprises a coumarin ring, a naphthalene ring with one or more hydrocarbon groups, and a five-membered hetero ring condensed with the naphthalene ring so as to give an electronic resonance through the coumarin and naphthalene rings releases a visible luminescence with a sutisfiable color purity and the luminescence consistently prolongs over a long period of time even at an elevated temperature when used in organic EL devices.

Particularly, this invention attains the above objective by providing an organic EL device which comprises the coumarin derivative represented by either General Formula 1 or 2:

(In General Formulae 1 and 2, X denotes carbon atom or a heteroatom. R¹ to R¹⁴ independently denote hydrogen atom or an arbitrary substituent, provided that R³ and/or R⁴ are apparently absent when R¹ and/or R² form a ring structure containing both the nitrogen atom linked with R¹ and/or R² and the carbon atom linked with R³ or R⁴. At least one of R⁹ to R¹⁴ is a hydrocarbon group which may bear a substituent. In case that X is a divalent or trivalent heteroatom, R⁷ and/or R⁸ are absent.)

This invention also attains the above objective by providing a display panel which uses such organic EL device.

In addition, this invention attains the above described objective by providing an information displaying equipment which uses such organic EL device.

Furthermore, this invention attains the above objective by providing a luminescent agent for use in organic EL device which comprises the coumarin derivative represented by either General Formula 1 or 2:

(In General Formulae 1 and 2, X denotes carbon atom or a heteroatom. R¹ to R¹⁴ independently denote hydrogen atom or an arbitrary substituent, provided that R³ and/or R⁴ are apparently absent when R¹ and/or R² form a ring structure containing both the nitrogen atom linked R¹ and/or R² and the carbon atom linked with R³ or R⁴. At least one of R⁹ to R¹⁴ is a hydrocarbon group which may bear a substituent. In case that X is a divalent or trivalent heteroatom, R⁷ and/or R⁸ are absent.)

Either of the coumarin derivatives represented by General Formula 1 or 2 is a novel organic compound which has not been documented in literatures. This invention is based on the creation of novel organic compounds, as well as on the discovery of their properties useful in industries.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a brief figure of an example for organic EL device according to this invention.

FIG. 2 is a brief figure of an example for display panel according to this invention.

FIG. 3 is a block diagram of an example for information displaying equipment according to this invention.

In the Figures, the reference numerals 1 and 10 represent substrates; 2 and 14, anodes; 3 and 16, hole transportation layers; 4 and 18, luminescent layers; 5, an electron transportation layer; 6 and 20, cathodes; 30, a dc source; 32 and 34, voltage-elevating circuits; 36 and 46, driving circuits; 38, a microcomputer; 40, a clock pulse-generating circuit; 42 and 44, oscillating circuits; and 48, a display panel.

BEST MODE FOR CARRYING OUT THE INVENTION

The following is to explain embodiments according to this invention: As mentioned heretofore, this invention relates to an organic EL device using the coumarin derivative represented by either General Formula 1 or 2.

In General Formula 1 and 2, X denotes carbon atom or a heteroatom. As to the heteroatom in X, usually, one can choose an atom of the group 15 or 16 in the periodic chart of elements, such as nitrogen, oxygen, sulfur, selenium and tellurium atoms. Among these carbon and heteroatoms, carbon, nitrogen, oxygen and sulfur atoms are preferable because coumarin derivatives with such atom are superior in optical properties and producibilities.

R¹ to R¹⁴ in General Formulae 1 and 2 independently denote hydrogen atom or an arbitrary substituent. The substituents in R¹ to R¹⁴ are, for example, aliphatic hydrocarbon groups with a carbon number of up to 20, such as methyl, ethyl, propyl, isopropyl, isopropenyl, 1-propenyl, 2-propenyl, butyl, isobutyl, sec-butyl, tert-butyl, 2-butenyl, 1,3-butadienyl, pentyl, isopentyl, neopentyl, tert-pentyl, 1-methylpentyl, 2-methylpentyl, 2-pentenyl, hexyl, isohexyl, 5-methylhexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and octadecyl groups; alicyclic hydrocarbon groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexenyl and cyclopeptyl groups; aromatic hydrocarbon groups such as phenyl, o-tolyl, m-tolyl, p-tolyl, xylyl, mesityl, o-cumenyl, m-cumenyl, p-cumenyl, benzyl, phenethyl and biphenylyl groups; ether groups such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, phenoxy and benzyloxy groups; ester groups such as ethoxycarbonyl, propoxycarbonyl, acetoxy and benzoyloxy groups; halogen groups such as fluoro, chloro, bromo and iodo groups; hydroxy group; carboxy group; cyano group; nitro group; and combinations thereof.

Dependently upon uses, it is preferable to choose as substituents in R¹ and R² an aliphatic, alicyclic, aromatic hydrocarbon or combination thereof, while those in R⁶, for example, short-chain aliphatic hydrocarbon groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl and tert-pentyl groups; ether groups such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, phenoxy and benzyloxy groups; ester groups such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, acetoxy and benzoyloxy groups; and cyano group: One or more hydrogen atoms in these substituents may be substituted by halogen group(s) such as fluoro group. As mentioned heretofore, at least one of the substituents in R⁹ to R¹⁴ is a hydrocarbon group such as aliphatic, alicyclic or aromatic hydrocarbon groups or a combination thereof: Among these, it is preferable to choose an aliphatic hydrocarbon group, in particular, an aliphatic hydrocarbon group having a branched-chain structure and a carbon number of up to 6, such as isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, 1-methylpentyl, 2-methylpentyl and isohexyl groups. As to the substituents in R⁷ and R⁸, it is preferable to choose an aliphatic, alicyclic or aromatic hydrocarbon group or a combination thereof similar to those in R¹ and R², provided that X is a divalent or trivalent heteroatom, and R⁷ and/or R⁸ are absent. In case that the carbon linked with R³ and/or R⁴ forms no ring structure such as piperidine or julolidine ring, one can choose as R³ and/or R⁴ hydrogen atom or an arbitrary substituent as described above, dependently upon uses. As to R⁵, one can choose hydrogen atom or hydroxyl group because coumarin derivatives therewith are superior in producibility, and alternatively an ether or ester group as described above while considering the uses of coumarin derivatives.

In certain applications such as organic EL device where luminescence-releasing ability is one of important factors, it is preferable to choose a coumarin derivative as represented by General Formula 3 or 4, where both R¹ and R² are aliphatic hydrocarbon groups which are in the linkage with the carbon atom bound to either R³ or R⁴ to form julolidine ring. In General Formulae 3 and 4, X denotes carbon or a heteroatom similarly as in General Formula 1 or 2, while R⁵ to R¹⁴ denote hydrogen or an arbitrary substituent similarly as in General Formula 1 or 2, and at least one of R⁹ to R¹⁴, a hydrocarbon group. R¹⁵ to R¹⁸ independently denote hydrogen or an aliphatic hydrocarbon group: Among these, it is preferable to choose as aliphatic hydrocarbon group a short-chain aliphatic hydrocarbon group such as methyl, ethyl, propyl, butyl or pentyl group. Among the coumarin derivatives represented by General Formula 3 or 4, those where at least one of R⁹ to R¹⁴ is a branched aliphatic hydrocarbon group such as isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, 1-methylpentyl, 2-methylpentyl or isohexyl group are characterized in that they are superior in luminescence abilities and solubilities in usual organic solvents, as well as in that their luminescent abilities are hardly weakened even under conditions where elevated temperatures are unavoidable because they are high in glass transition points and therefore large in thermal stability.

The coumarin derivatives represented by Chemical Formulae 1 to 27 are illustrative for those feasible in this invention. These have a maximum for luminescence such as fluorescence in the visible region at a wavelength of around 520 nm, usually, 490 nm to 560 nm: When excited, the coumarin derivatives give a visible light emission in the bluish to yellowish green region. Many of the coumarin derivatives represented by General Formula 1 or 2 are significantly higher in glass transition point (130° C. or higher), in particular, 150° C. or higher dependently upon substituents as seen in the coumarin derivative represented by Chemical Formula 18. The glass transition point of the coumarin derivative according to this invention can be determined by, for example, usual differential scanning calorimetry (abbreviated as “DSC analysis” hereinafter) as described later.

The coumarin derivatives feasible in this invention can be prepared in various ways: With an economical viewpoint, it is preferable to employ a process containing the step of allowing the compound represented by General Formula 5 which has R¹ to R⁶ corresponding to those in General Formula 1 or 2 to react with the compound represented by General Formula 6 or 7 which has R⁷ to R¹⁴ corresponding to those in General Formula 1 or 2. In General Formula 6 or 7, in case that X is a divalent or trivalent heteroatom, H¹ and H² are absent.

Particularly, adequate amounts (usually, roughly equimolar amounts) of the compound represented by General Formula 5 and the compound represented by General Formula 6 or 7 are placed in a reaction vessel, dissolved in an appropriate solvent, if necessary, admixed with either a basic compound, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, sodium acetate, ammonia, triethylamine, piperidine, pyridine, pyrrolidine, aniline, N,N-dimethylaniline or N,N-diethylaniline, an acidic compound such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, acetic anhydride, trifluoroacetic acid, p-toluenesulfonic acid, methanesulfonic acid or trifluromethanesufonic acid or a Lewis acidic compound such as aluminium chloride, zinc chloride, tin tetrachloride or titanium tetrachloride, and then allowed to react at an ambient or higher temperature while stirring under refluxing conditions.

As to solvents, one can choose hydrocarbons such as pentane, hexane, cyclohexane, octane, benzene, toluene and xylene; halides such as carbon tetrachloride, chloroform, 1,2-dichloroetane, 1,2-dibromoethane, trichloroetylene, tetrachloroethylene, chlorobenzene, bromobenzene and α-dichlorobenzene; alcohols and phenols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, isopentyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 2-methoxyethanol, phenol, benzyl alcohol, cresole, diethylene glycol, triethylene glycol and glycerin; ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, anisole, 1,2-dimethoxyethane, diethylene glycol dimethyl ether, dicyclohexyl-18-crown-6, methylcarbitol and ethylcarbitol; acids and acid derivatives such as acetic acid, acetic anhydride, trichloroacetic acid, trifluoroacetic acid, propionic anhydride, ethyl acetate, butyl carbonate, ethylene carbonate, propylene carbonate, formamide, N-methylformamide, N,N-dimethylformamide, N,N-dimethylacetoamide, hexamethylphosphoric triamide and phosphoric trimethyl; nitriles such as acetonitrile, propionitrile, succinonitrile and benzonitrile; nitro compounds such as nitromethane and nitrobenzene; sulfur-containing compounds such as dimethylsulfoxide and sufolane; and water which may be used in combination, if necessary.

In case of using solvents, generally, a larger amount of solvent leads to a less reaction efficiency, while a less amount of solvent, a more difficulty in homogenous heating and stirring and also a more liability of side reactions. Thus, it is desirable to set the amount of solvent to a level of up to 100-folds, usually, 5 to 50-folds by weight against the total amounts of material compounds to be used. The reaction completes within 10 hours, usually, 0.5 to 5 hours, dependently upon the type of material compounds and reaction conditions. The progress of reaction can be monitored by conventional method, for example, thin layer chromatography, gas chromatography and high-performance liquid chromatography. The coumarin derivatives feasible in this invention are obtainable in a good yield by or in accordance with such process. The compounds represented by General Formulae 5 to 7 are obtainable by usual methods which are to prepare analogous compounds.

Prior to uses, the coumarin derivatives thus obtained are usually purified with a method(s) usually employed in the purification of analogous compounds, such as dissolution, extraction, separation, decantation, filtration, concentration, thin layer chromatography, column chromatography, gas chromatography, high-performance liquid chromatography, distillation, sublimation and crystallization which may be applied in combination, if necessary. Dependently upon the type of coumarin derivatives and uses of organic EL devices, it is desirable to highly purify coumarin derivatives with distillation, crystallization and/or sublimation, prior to their use.

Among these, sublimation is superior to others because high-purity crystals can be easily obtained through a single step with a less loss for coumarin derivatives during purification, as well as because solvent is not incorporated in crystals. Although both atmospheric and reduced pressure sublimation methods are applicable to this invention, the latter method is usually employed. To sublimate coumarin derivatives in vacuo, for example, an adequate amount of a coumarin derivative is placed in a sublimation purification apparatus, and then heated at the possible lowest temperature, in particular, at a temperature lower than its melting point while keeping the pressure inside the apparatus at 10⁻² Torr or lower, desirably, 10⁻³ Torr or lower so that the coumarin derivative does not cause decomposition. When the purity of a coumarin derivative to be subjected to sublimation purification is lower, the sublimation rate is reduced so as to avoid the incorporation of impurities by increasing or decreasing the pressure and/or heating temperature in the apparatus, while the sublimation is accelerated by aerating the inner space of the apparatus with an inert gas such as rare gas when a coumarin derivative is less sublimatable. The size of crystals obtained by sublimation can be controlled by elevating or reducing temperature at the condensation surface in the apparatus: When the condensation surface is kept at a temperature slightly lower than heating temperature so that the coumarin derivative gradually crystallizes, one can obtain crystals of a larger size.

The coumarin derivatives according to this invention are very advantageously usable as luminescent agent which is used alone or in combination with other luminescent compounds so as to allow an organic EL device to emit a visible light in the green region because, as described heretofore, they give a maximum for luminescence such as fluorescence in the visible region at a wavelength of around 520 nm, usually, 490 to 560 nm, a visible emission in the bluish to yellowish green region when excited, and a stable thin membrane in a glass state, as well as because many of them exhibit a large thermal resistance. The wording “organic EL device(s)” as referred to as in this invention means electroluminescent devices in general which use such coumarin derivative as luminescent agent: One of the most important targets to which this invention is applied is an organic EL device of mono- or multi-layer type comprising a cathode to be energized with a positive voltage, an anode to be energized with a negative voltage, a luminescent layer where hole and electron are allowed to recouple each other so as to obtain a luminescence, and arbitrarily a hole injection/transportation layer for injecting and transporting holes from the cathode, an electron injection/transportation layer for injecting and transporting electrons from the anode, and a hole-blocking layer for suppressing the transportation of holes from the luminescent layer to the electron injection/transportation layer.

As well known in the art, the action mechanism of organic EL devices essentially consists of the steps of injecting electrons and holes from electrodes, allowing the electrons and holes to move in solids, allowing the electrons and holes to recouple to give singlet or triplet excitons, and allowing the excitons to emit a luminescence: Mono- and multi-layered organic EL devices are essentially indifferent each other in these steps. However, in mono-layered organic EL devices, the characteristics of the above four steps can not be improved if one changes the molecular structure of luminescent compounds, while in multi-layered organic EL devices, the properties required in each step can be distributed to a plurality of materials which are independently optimized: Thus, multi-layered organic EL devices attain a prescribed performance more easily than mono-layered organic EL devices.

Because of these, the organic EL device of this invention will be explained hereinafter with reference to an example of multi-layered organic EL device. FIG. 1 is a brief figure of an example for multi-layered organic EL device according to this invention. In FIG. 1, the reference numeral 1 represents a substrate which is formed by preparing a substrate material including a glass such as aluminosilicate glass, aluminoborosilicate glass, silica glass, soda lime glass, barium silicate glass, barium borosilicate glass or borosilicate glass; a plastic such as aramid, acrylic resin, polyallylate, polyimide, polyurethane, polyetherketone, polyethersulfone, polyester, polyethylene, poly (ethylene terephthalate), polyolef in, polycarbonate, polysulfone, poly (vinyl chloride), polypropylene, poly (methyl acrylate), epoxy resin, phenol resin, fluorine resin or melamine resin; or a ceramic such as alumina, silicon, silica or silicon carbide into a plate, sheet or film which may be laminated each other, if necessary. Preferred substrate materials are a glass for photomask such as aluminosilicate glass, aluminoborosilicate glass, silica glass, borosilicate glass and barium borosilicate glass which are low in both alkali content and thermal expansion coefficient, plane and free of scratches on their surface and easily grindable; and plastics such as aramids, epoxys, phenols, polyallylates, polyimides, polyesters, aromatic polyethers, polyolef ins, melamines and fluorines which are superior in affinity to adjacent electric conductive membrane and less in moisture permeability, while opaque ceramic materials such as silicon may be used in combination with transparent electrode material (s). When it is necessary to control the chromaticity of luminescence, chromaticity adjusting means such as filter membrane, chromaticity conversion membrane and dielectric reflection membrane is provided in an appropriate part of the substrate 1.

The reference numeral 2 represents an anode, which is formed by preparing one or more metals or electric conductive compounds low in electric resistivity and high in optical transmissivity throughout the visible region into a single or plurality of membrane(s) with a thickness of 10 to 1,000 nm, desirably, 50 to 500 nm to give an electric resistivity of 1 kΩ/□ or lower, desirably, 5 to 50 Ω/□ for the anode 2 by a method such as vacuum deposition, spattering, chemical vapor deposition (CVD), atom layer epitaxy (ALE), embrocation or immersion while allowing the membrane(s) to contact with either surface of the substrate 1. Examples of electric conductive materials feasible in the anode 2 are metals such as gold, platinum, aluminium and nickel; metal oxides such as zinc oxide, tin oxide, indium oxide and mixtures of tin oxide and indium oxide (abbreviated as “ITO” hereinafter); and electric conductive oligomers and polymers of repeating aniline, thiophene or pyrrole units. Among these, ITO is characterized in that one can easily obtain preparations with a reduced resistivity, as well as in that minute patterns can be easily provided by etching it with acids.

The reference numeral 3 represents a hole injection/transportation layer, which is usually formed with a method similar to that in the anode 2 by preparing the hole injection/transportation layer material into a membrane with a thickness of 1 to 1,000 nm while allowing it to contact with the anode 2. As to hole injection/transportation layer materials, it is desirable to choose a material which exhibits a low ionization potential and a hole mobility of, for example, at least 10⁻⁶ cm²/V second under an electric field of 10⁴ to 10⁶ V/cm so as to facilitate the injection and transportation of holes from the anode 2. Particular hole injection/transportation layer materials are, for example, arylamine, imidazole, oxadiazole, oxazole, triazole, chalcone, styryl anthracene, stilbene, tetraarylethene, triarylamine, triarylethene, triarylmethane, phthalocyanine, fluorenone, hydrazone, N-vinylcarbazole, pyrazoline, pyrazolone, phenylanthracene, phenylenediamine, polyarylalkane, polysilane, polyphenylenevinylene and porphyrin derivatives which are usually used in organic EL devices: These may be used in combination, if necessary. Among these, the much more preferable are monomers and polymers in an aromatic tertiary amine form which are of an arylarnine such as monoarylamine, diarylamine, triarylamine and tetraarylamine.

The reference numeral 4 represents a luminescent layer, which is usually formed with a method similar to that in the anode 2 by preparing one or more coumarin derivatives of this invention into a membrane with a thickness of 10 to 1,000 nm, preferably, 10 to 200 nm while allowing it to contact with the hole injection/transportation layer 3. The coumarin derivative of this invention provides organic EL devices which are suitable for practical uses even when used alone in the formation of luminescent layer because it easily forms excitons such as singlet and triplet excitons, as well as because it is adequate in energy levels for luminescences such as fluorescence and phosphorescence and also less liable to “concentration quenching” for luminescence due to luminescent layer materials. This invention however never prevents combined uses with host compound(s) which may be used for particular applications: In this case, the coumarin derivative of this invention and a usual host compound are prepared into a single or adjacent separate membrane(s) with a thickness of 1 to 1,000 nm, preferably, 10 to 200 nm, thus forming the luminescent layer 4. In case of using a host compound in combination, the coumarin derivative according to this invention is used in an amount of up to equimolar to the host compound(s), usually, 0.1 to 10 mol %, desirably, 0.5 to 5 mol % against the host compound(s).

As to host compounds or other luminescent compounds to be used in combination with the coumarin derivative according to this invention when it is used as guest compounds, one can choose quinolinol metal complexes which are usual in organic EL device and, for example, condensed polycyclic aromatic hydrocarbons such as anthracene, chrysene, coronene, triphenylene, naphthacene, naphthalene, phenantlene, picene, pyrene, fluorene, perylene, benzopyrene and their derivatives; hydrocarbon ring assemblies such as quaterphenyl, 1,4-diphenylbutadiene, terphenyl, stilbene, tetraphenylbutadiene, biphenyl and their derivatives; heterocyclic compounds such as oxadiazole, carbazole, pyridazine, benzimidazole, benzoxazole, benzothiazole and their derivatives; quinacridone, rubrene compounds and their derivatives; and polymethyne dyes of styryl type.

Preferable host compounds are quinolinol metal complexes: The wording “quinolinol metal complex(es)” as referred to as in this invention means complexes in general comprising a quinolinol, such as 8-quinolinol and benzoquinoline-10-ol, which bears in the same molecule a pyridine residue and hydroxyl group and behaves as ligand; and a univalent, divalent or trivalent metal or its oxide of the group 1, 2, 12 or 13 in the periodic chart of elements, such as lithium, sodium, potassium, beryllium, magnesium, calcium, zinc, boron, aluminium, gallium and indium, which behaves as center metal and receives an electron pair from the nitrogen atom in the pyridine residue to form a coordinate bond with the ligand. In case that ligand is either 8-quinolinol or benzoquinoline-10-ol, it may bear one or more substituents, never hindering one or more substituents, for example, halogen groups such as fluoro, chloro, bromo and iodo groups; aliphatic hydrocarbon groups such as methyl, trifluoromethyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl and tert-pentyl groups; ether groups such as methoxy, trifluoromethoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, isopentyloxy, hexyloxy, phenoxy and benzyloxy groups; ester groups such as acetoxy, trifluoroacetoxy, benzoylacetoxy, methoxycarbonyl, trifluoromethoxycarbonyl, ethoxycarbonyl and propoxycarbonyl groups; cyano group; nitro group and sulfone group to be bound to carbon(s) other than those at the 8- or 10-positions to which hydoxyl group(s) is linked. In case that a quinolinol metal complex has two or more ligands in the same molecule, they may be the same or different each other.

Particular quinolinol metal complexes are, for example, aluminium complexes such as aluminium-tris(8-quinolinolato), aluminium-tris(3,4-dimethyl-8-quinolinolato), aluminium-tris(4-methyl-8-quinolinolato), aluminium-tris(4-methoxy-8-quinolinolato), aluminium-tris(4,5-dimethyl-8-quinolinolato), aluminium-tris(4,6-dimethyl-8-quinolinolato), aluminium-tris(5-chloro-8-quinolinolato), aluminium-tris(5-bromo-8-quinolinolato), aluminium-tris(5,7-dichloro-8-quinolinolato), aluminium-tris(5-cyano-8-quinolinolato), aluminium-tris(5-sulfonyl-8-quinolinolato), aluminium-tris(5-propyl-8-quinolinolato) and aluminium-tris(2-methyl-8-quinolinolato); zinc complexes such as zinc-bis(8-quinolinolato), zinc-bis(2-methyl-8-quinolinolato), zinc-bis(2,4-dimethyl-8-quinolinolato), zinc-bis(2-methyl-5-chloro-8-quinolinolato), zinc-bis(2-methyl-5-cyano-8-quinolinolato), zinc-bis(3,4-dimethyl-8-quinolinolato), zinc-bis(4,6-dimethyl-8-quinolinolato), zinc-bis(5-chloro-8-quinolinolato) and zinc-bis(5,7-dichloro-8-quinolinolato); beryllium complexes such as beryllium-bis(8-quinolinolato), beryllium-bis(2-methyl-8-quinolinolato), beryllium-bis(2,4-dimethyl-8-quinolinolato), beryllium-bis(2-methyl-5-chloro-8-quinolinolato), beryllium-bis(2-methyl-5-cyano-8-quinolinolato), beryllium-bis(3,4-dimethyl-8-quinolinolato), beryllium-bis(4,6-dimethyl-8-quinolinolato), beryllium-bis(5-chloro-8-quinolinolato), beryllium-bis(4,6-dimethyl-8-quinolinolato) and beryllium-bis(10-hydroxybenzo [h] quinolinolato); magnesium complexes such as magnesium-bis(8-quinolinolato), magnesium-bis(2-methyl-8-quinolinolato), magnesium-bis(2,4-dimethyl-8-quinolinolato), magnesium-bis(2-methyl-5-chloro-8-quinolinolate), magnesium-bis(2-methyl-5-cyano-8-quinolinolato), magnesium-bis(3,4-dimethyl-8-quinolinolato), magnesium-bis(4,6-dimethyl-8-quinolinolato), magnesium-bis(5-chloro-8-quinolinolato) and magnesium-bis(5,7-dichloro-8-quinolinolato); indium complexes such as indium-tris(8-quinolinolato); gallium complexes such as gallium-tris(5-chloro-8-quinolinolato); and calcium complexes such as calcium-bis(5-chloro-8-quinolinolato) which may be used in combination, if necessary. The above host compounds are listed only for illustration, and intended in no way to limit to these the host compounds feasible in this invention.

The reference numeral 5 represents an electron injection/transportation layer, which is usually formed with a method similar to that in the anode 2 by preparing one or more organic compounds which are high in electron affinity or anthraquinodimethane, anthrone, oxadiazole, carbodiimide, distyrylpyrazine, diphenylquinone, silazane, thiopyrandioxide, triazole, tetracarboxylic acid derivative of heterocyclic compound, phthalocyanine, fluorene derivatives, quinolinol metal complexes similar to that in the luminescent layer 4 or a conductive oligomer or polymer of repeating aniline, thiophen or pyrrole units into a membrane with a thickness of 10 to 500 nm while allowing it to contact with the luminescent layer 4. In case that a plurality of the electron injection/transportation layer materials are used, they may be mixed to homogeneity and then formed into a single layer, and alternatively formed into a plurality of separate layers without premixing the material while allowing each layer to contact with the adjacent layer. In case of providing a hole-blocking layer, a hole-blocking layer material, for example, oxadiazole compound such as 2-biphenyl-4-yl-5-(4-tert-butylphenyl)-[1,3,4]oxadiazole, 2,2-bis[5-(4-biphenyl) -1,3,4-oxadiazole-2-yl-1,4-phenylene]hexafluoropropane and 1,3,5-tris- (2-naphthalene-1-yl-[1,3,4]oxadiazole-5-yl)benzene is prepared with a method similar to that in the anode 2 while allowing it to contact with the luminescent layer 4, prior to the formation of the electron injection/transportation layer 5. The thickness of such hole-blocking layer is set to a level in the range of 1 to 100 nm, usually, 10 to 50 nm while considering the thickness of the electron injection/transportation layer 5 and the operation characteristics of organic EL devices.

The reference numeral 6 represents a cathode, which is usually formed by depositing one or combined metals such as lithium, magnesium, calcium, sodium, potassium, silver, copper, aluminium, indium, ytterbium, their alloys and metal oxides and electric conductive compounds with a work function (usually not higher than 5 eV) lower than that for the compound to be used in the electron injection/transportation layer 5 so that the resultant layer comes into contact with the electron injection/transportation layer 5. There is provided no limitation for the thickness of the cathode 6: It is set to 10 nm or more thick, desirably, 50 to 500 nm and also give a resistivity of 1 kΩ/□ or lower while considering electric conductivity, production cost, thickness of device, and optical transmittance. There may be provided an interfacial layer of aromatic diamine, quinaqcridone, naphthacene, organic silicon or organic phosphide between the cathode 6 and electron injection/transportation layer 5 in order to improve their adhesion, if necessary. Furthermore, to facilitate the transportation of electrons from the cathode 6 to the injection/transportation layer 5, there may be provided with a method similar to that in the anode 2 a membrane of alkaline metal or alkaline earth metal compound such as lithium fluoride or lithium oxide, 0.1 to 2 nm thick, on the side of the cathode 6 which is in contact with the electron injection/transportation layer 5.

As explained heretofore, the organic EL device of this invention can be obtained by providing in one device an anode, luminescent layer, cathode and arbitrarily a hole injection/transportation layer, electron injection/transportation layer, and/or hole-blocking layer on the same substrate while allowing each layer to contact with adjacent layer(s). During the formation of each layer, it is desirable to carry out all the working steps under highly vacuumed conditions, particularly, at a pressure of 10⁻⁵ Torr or lower to minimize the oxidation and decomposition of organic compounds, as well as to minimize the adhesion of oxygen and water. In the formation of a luminescent layer, the ratio of host and guest compounds can be adjusted by premixing them in a prescribed ratio, and alternatively by separately controlling the heating velocities for respective compounds in vacuum sublimation. To minimize deterioration under operation conditions, it is desirable either to seal a part or whole of the organic EL device thus obtained with a sealing glass or metallic cap in the stream of an inert gas, or to coat or cover it with a moisture-proof paint or protecting membrane such as those of ultraviolet-setting resins. Dependently upon the structure of organic EL devices, in order to allow the luminescent layer to release a luminescence outside the device in an improved efficiency, one can employ one or combined diffracting means which change the incident angle of the luminescence against the luminescence-releasing plane in the device, for example, bracelet plates and reflection or transmission gratings of one- or two-dimensional type to suppress the total reflection at the interface between the organic and inorganic layers in the devices and/or the luminescence-releasing plane and the air.

Now, explanation is made on the way of using the organic EL device of this invention. The organic EL device is driven by intermittently energizing it with a relatively high pulse voltage, or continuously energizing it with a relatively low non-pulse voltage, usually, 2 to 50 V, dependently upon its uses. The organic EL device of this invention gives luminescence only when anode potential exceeds cathode potential. Thus, both dc or ac voltages are feasible to energize the organic EL devices of this invention, and the waveform and the frequency of such voltages are arbitrary selected. When energized with ac, the organic EL device of this invention increases and decreases the brightness of luminescence, and repeats on/off of luminescence due to its principle. In case of the organic EL device in FIG. 1, when a voltage is energized between the anode 2 and the cathode 6, holes injected from the anode 2 move into the luminescent layer 4 through the electron injection/transformation layer 3, and electrons injected from the cathode 6 move into the luminescence layer 4 through the electron injection/transportation layer 5. As the result, the holes and electrons recouple in the luminescent layer 4, and the prescribed luminescence is released from coumarin derivatives in the excited state through the anode 2 and the substrate 1. Dependently upon the structure and the ratio of host compound to be used in combination with the coumarin derivative, the organic EL device of this invention has a maximum for luminescence such as fluorescence in the visible region at a wavelength around 520 nm, usually, in the green region at a wavelength of 490 to 560 nm. The x value for such luminescence is usually in the range of 0.2 to 0.5, and the y value, in the range of 0.3 to 0.8 on the xy chromaticity diagram established by the Commission International de I'Eclairage (CIE).

The organic EL device of this invention would find a variety of uses in illuminants and information displaying equipments to visualize informations because it is superior in durability, high in emission efficiency and as the result easy to elevate its brightness. Particularly, since the illuminants using the organic EL device of this invention as light source can be saved for power consumption and formed into a light panel form, they are very useful in illuminants in general, in addition to the uses as energy- and space-saving lighting source or information displaying device, for example, those in liquid crystal devices, copying apparatuses, printing apparatuses, electronic photographic apparatuses, computers and application apparatuses, controlling instruments directed to industrial uses, electronic measuring apparatuses, analyzing apparatuses, measuring instruments in general, communicating apparatuses, electronic measuring instruments directed to uses in medical treatment; electronic equipments in general which are directed to uses at home or professional uses; cars, automobiles, ships, airplanes and spaceships; and aircraft controlling apparatuses, interiors, signboards and signs. In case that the organic EL device in this invention is used as displaying means in information displaying equipments such as measuring instruments to be equipped to cars, automobiles, ships, aircrafts and spaceships, computers, televisions, video recorders, computerized game consoles, clocks, calculators, telephones, telecommunicating apparatuses, car navigation systems, osilloscopes, radars, sonars, signs and signboards, the organic EL device may be driven by applying thereto with a driving circuit of conventional simple or active matrix types which is usually in this art while combining with other organic EL devices which release a visible luminescnce in the blue, green or red region, and/or appropriate filters which are to control luminescent chromaticity and color tone, if necessary.

By the way, the coumarin derivative according to this invention is feasible in uses as chromaticity-adjusting material which is to control chromaticity of luminescence by an organic EL device to a desired level in addition to those as luminescent layer material in the organic EL devices because it has an absorption maximum in the visible region at a wavelength around 470 nm, usually, 440 to 500 nm, and also a large molecular absorption coefficient (abbreviated as “ε” hereinafter) of 1×10⁴ or larger, desirably, 3×10⁴ or larger. Thus, the wording “organic EL device(s)” as referred to in this invention means organic EL device in general where with the purpose of controlling the chromaticity of electroluminescence in luminescent compounds, the specific coumarin derivatives are used alone or in combination with one or more other compounds having light-absorbing ability in addition to those which comprise specific coumarin derivatives as the luminescent layer materials.

The several embodiments according to this invention will be explained with reference to Examples:

EXAMPLE 1

Luminescent Agent for Use in Organic EL Device

An adequate amount of dimethylsulfoxide was placed in a reaction vessel and mixed with 0.21 g of the compound represented by Chemical Formula 28 and 0.21 g of the compound represented by Chemical Formula 29. The mixture was refluxed for two hours, cooled to ambient temperature and admixed with an adequate amount of methanol, followed by collecting the resultant crystals by filtration. The crystals were purified on column chromatography using a mixture of chloroform and ethyl acetate as eluent to obtain the coumarin derivative of this invention represented by Chemical Formula 18 in 0.2 g orange crystals.

A part of the crystals was sampled, revealing that the coumarin derivative in this Example showed a melting point of 345 to 351° C. The visible absorption and fluorescence emission spectra determined in usual manner in methylene chloride solution showed an absorption maximum(ε=5.8×10⁴) and a fluorescent maximum at wavelengths of 491 and 518 nm, respectively. The ¹H-nuclear magnetic resonance spectrum (abbreviated as “¹H-NMR Spectrum” hereinafter) in chloroform deuteride solution showed peaks at chemical shifts δ (ppm, TMS) of 1.37 (6H, s), 1.56 (9H, s), 1.62 (6H, s), 1.79 (2H, s), 1.85 (2H, s), 3.30 (2H, t), 3.39 (2H, s), 7.40 (1H, s), 7.67 (1H, dd), 7.73 (1H, d), 7.90 (1H, d), 7.91(1H, d), 8.91 (1H, s) and 9.02 (1H, s) when determined in usual manner.

Another part of the crystals was sampled and subjected to usual DSC analysis using a commercially available DSC analyzing system, Traded name of “Model DSC 220U”, a product of Seiko Instruments Incorporated., leading to a glass transition point at 151° C. Simultaneously, the conventional analogous compound represented by Chemical Formula 30 where the naphtothiazole ring beared no hydrocarbon group was determined for its glass transition point (129° C.) similarly as above. Although the analogous compound represented by Chemical Formula 30 was significantly lower in solubility in organic solvents such as acetone and chloroform in comparison with the coumarin derivative represented by Chemical Formula 18 according to this invention, the analogous compound exhibited a luminescent maximum in a similar wavelength region as that in the coumarin derivative represented by Chemical Formula 18.

As well known, glass transition point is one of the important merkmals which are to estimate the thermal stability of organic compounds: It has been documented that a compound with a higher glass transition point marks a larger thermal stability. The above experimental results show that the coumarin derivative of this invention, which has a condensed naphthalene ring linked with one or more hydrocarbon groups in the molecule, remarkably improves the thermal resistance of conventional analogous compound without substantially changing their desirable optical properties.

The highly heat-resistant coumarin derivative of this Example which give maxima for absorption and fluorescence in the visible region, and also a visible emission in the green region when excited is useful for luminescent layer material and chromaticity-adjusting material in organic EL devices.

EXAMPLE 2

Luminescent Agent for Use in Organic EL Device

The compound represented by Chemical Formula 31 in place of the compound represented by Chemical Formula 28 was allowed to react in accordance with the method in Example 1 to obtain the coumarin derivative represented by Chemical Formula 24 according to this invention.

The highly heat-resistant coumarin derivative of this Example which give maxima for absorption and fluorescence in the visible region, and also a visible emission when excited is useful for luminescent layer material and chromaticity-adjusting material in organic EL devices.

EXAMPLE 3

Luminescent Agent for Use in Organic EL Device

The compounds represented by Chemical Formulae 32 and 33 in place of those represented by Chemical Formulae 28 and 29 respectively were allowed to react in accordance with the method in Example 1 to obtain the coumarin derivative of this Example represented by Chemical Formula 12.

The highly heat-resistant coumarin derivative of this Example which give maxima for absorption and fluorescence in the visible region, and also a visible emission when excited is useful for luminescent layer material and chromaticity-adjusting material in organic EL devices.

EXAMPLE 4

Luminescent Agent for Use in Organic EL Device

The compounds represented by Chemical Formulae 34 and 33 in place of those represented by Chemical Formulae 28 and 29 respectively were allowed to react in accordance with the method of Example 1 to obtain the coumarin derivative represented by Chemical Formula 11 according to this invention.

The highly heat-resistant coumarin derivative of this Example which give maxima for absorption and fluorescence in the visible region, and also a visible emission when excited is useful for luminescent layer material and chromaticity-adjusting material in organic EL devices.

EXAMPLE 5

Luminescent Agent for Use in Organic EL Device

The compounds represented by Chemical Formulae 35 and 36 in place of those represented by Chemical Formulae 28 and 29 respectively were allowed to react in accordance with the method in Example 1 to obtain the coumarin derivative represented by Chemical Formula 2 according to this invention.

The highly heat-resistant coumarin derivative of this Example which give maxima for absorption and fluorescence in the visible region, and also a visible emission when excited is useful for luminescent layer material and chromaticity-adjusting material in organic EL devices.

EXAMPLE 6

Luminescent Agent for Use in Organic EL Device

A 50 ml aliquot of N,N-dimethylformamide was placed in a reaction vessel and mixed with 13.4 g of the compound represented by Chemical Formula 37 and 11.0 g of the compound represented by Chemical Formula 28. The mixture was refluxed for two hours, cooled to ambient temperature and admixed with an adequate amount of methanol, followed by collecting the resultant crystals by filtration. The crystals were purified on column chromatography using chloroform as eluent to obtain the coumarin derivative of this invention represented by Chemical Formula 20 in 8.0 g yellow orange crystals.

A part of the crystals was sampled and determined in usual manner, revealing that the coumarin derivative in this Example showed a melting point of 251 to 254° C. DSC analysis similar to that in Example 1 showed a glass transition point at 131° C. The visible absorption and fluorescence emission spectra in methylene chloride solution showed an absorption maximum (ε=4.2×10⁴) and a fluorescent maximum at wavelengths of 453 and 519 nm, respectively when determined in usual manner. The ¹H-NMR Spectrum in chloroform deuteride solution showed peaks at chemical shifts δ (ppm, TMS) of 1.37 (6H, s), 1.50 (9H, s), 1.57 (6H, s), 1.78 to 1.87 (4H, m), 3.11 (4H, m), 3.25 to 3.29 (2H, m), 3.34 to 3.38 (2H, m), 7.57 (1H, s), 7.66 (1H, dd), 7.75 (1H, d), 7.89 to 7.94(2H, m) and 8.84 (1H, s) when determined in usual manner.

The highly heat-resistant coumarin derivative of this Example which give maxima for absorption and fluorescence in the visible region, and also a visible emission in the green region when excited is useful for luminescent layer material and chromaticity-adjusting material in organic EL devices.

EXAMPLE 7

Luminescent Agent for Use in Organic EL Device

Either of six distinct coumarin derivatives, obtained by the methods in Examples 1 to 6, was placed in a water-cooled sublimation apparatus and then heated while keeping the inner space of the apparatus at a reduced pressure in usual manner to effect sublimation purification.

The coumarin derivatives in this Example are useful for luminescent layer and chromaticity-adjusting materials in organic EL devices which need highly purified luminescent organic compounds.

Although the coumarin derivatives feasible in this invention, including those represented by Chemical Formulae 1 to 27 but none-specifically illustrated in Examples 1 to 7, are slightly different in starting reaction conditions and yields dependently on their structures, they can be obtained by the methods in Examples 1 to 7 or in accordance therewith.

EXAMPLE 8

Organic EL Device

A multi-layered organic EL device with the structure of FIG. 1 was prepared with the luminescent agent according to this invention: A glass substrate with a transparent ITO electrode, 160 nm thick, was patterned with a hydrobromic acid in usual manner, washed with organic alkali detergent, refined water, acetone and ethanol in the given order under ultrasonical conditions, dried, aerated with ultraviolet ozone to remove organic impurities on the surface of ITO electrode, and transferred to the pretreatment room in a vacuum depositing apparatus. The pretreatment room was reduced to an inner pressure of 1×10⁻⁶ Torr, injected with a mixture of argon and oxygen gases to give an inner pressure of 1×10⁻² Torr, and subjected to plasma treatment, thus obtaining a clean substrate 1 with ITO electrode as the cathode 2.

The substrate 1 was transferred to the organic vaporizing room in the vacuum depositing apparatus which had been reduced to an inner pressure of 5×10⁻⁷ Torr, while the surface of ITO electrode as the cathode 2 was attached with an organic membrane-forming mask, after which the carbon crucible was heated to deposit the copper phthalocyanine represented by Chemical Formula 38 and triphenylamine tetramer represented by Chemical Formula 39 (abbreviated as “TPTE” hereinafter) in this order as the hole injection/transportation layer materials to give respective thickness of 10 and 50 nm, thus forming the hole injection/transportation layer 3. Subsequently, either coumarin derivative represented by Chemical Formula 18 or 20 as a luminescent layer material, obtained by the method of Example 1 or 6, and tris(8-quinolinolate) were simultaneously deposited in the range of 0.5:100 to 1:100 in terms of the weight ratio to form the luminescent layer 4, thickness of 20 nm, which was in contact with the hole injection/transportation layer 3, after which Tris(8-quinolinolate) aluminium was deposited to form the electron injection/transportation layer 5, thickness of 40 nm, which was in contact with the luminescent layer 4.

Thereafter, the substrate 1 was transferred to the metal-depositing room in the vacuum depositing apparatus, deposited with lithium fluoride and aluminium in this order to give respective thickness of 0.5 and 150 nm to form the anode 6 which was in contact with the electron injection/transportation layer 5, after which the resultant device was sealed with a glass plate and ultraviolet-setting resin under nitrogen-aerating conditions, thus obtaining an organic EL device.

Separately, another organic EL device as control for comparison was prepared similarly as in the above except that a quinuclidone compound (N,N′-dimethylqunuclidone) represented by Chemical Formula 40 was used in place of the coumarin derivative of this invention. The quinuclidone compound represented by Chemical Formula 40 has a practical luminescent property and durability, and is one of typical luminescent layer materials in green light releasing devices. Three types of organic EL devices thus obtained were determined in usual manner for electroluminescent properties and life expectancies (or a driving time to halve initial brightness). In the determination of life expectancies, the initial brightness was set to 4,000 cd/m², in case that the determination was carried out at ambient temperature, while in the case of determination at 85° C., to 3,600 cd/m². The results were as shown in Table 1.

TABLE 1

Wavelength of Luminescent layer luminescent Chromaticity material maximum (nm) diagram (x, y) A B C D E Remarks Chemical Formula 18 526 (0.33, 0.61) 1,231 5.6 11.2 290 44 Present invention Chemical Formula 20 529 (0.33, 0.61) 1,361 6.6 12.4 240 10 Present invention Chemical Formula 40 544 (0.38, 0.56) 798 4.3 7.3 280 32 Control Note: The symbols “A”, “B”, “C”, “D”, and “E” mean “Luminescent brightness (cd/m²), “Power efficiency (lm/W)”, “Current efficiency (cd/A)”, “Life expectancy at ambient temperature (hour)”, and “Life expectancy at 85° C. (hour)”, respectively.

As seen from the results in Table 1, the organic EL devices in this Example and control organic EL device commonly exhibited a luminescent maximum in the green region at a wavelength of around 530 nm. The organic EL devices in this Example were narrow in half-band width for luminescence (65 to 70 nm), and were superior in color purity to those of the control organic EL device as evident from their color coordinates on the xy chromaticity diagram established by the CIE: The x and y value for the organic EL devices in this Example were 0.33 and 0.61 respectively, while in the control organic EL device, the x and y value were 0.38 and 0.56 respectively.

When energized with a dc voltage, the organic EL devices in this Example initiated luminescence around 3V, and the luminescence exceeded 20,000 cd/m² at 10V, and reached the highest brightness (130,000 cd/m²) around 14V. As seen in Table 1, the organic EL devices in this Example gave at ambient temperature a high luminescent brightness of 1,200 to 1,400 cd/m², and as the result, gave significantly high power and current efficiencies of about 6 lm/W and 11 to 12 cd/A respectively when driven with a constant current of 11 mA/cm². While the control organic EL device was significantly inferior to the organic EL devices in this Example in luminescent brightness (800 cd/m²) when driven similarly as above, and its power and current efficiencies are lower (4.31 m/W and 7.3 cd/A) than those in the organic EL devices.

As to life expectancy, as seen in Table 1, the organic EL devices in this Example gave prolonged expectancy exceeding 200 hours when set to an initial brightness of 4,000 cd/m² and driven at ambient temperature with a constant current, and non-luminescent parts such as dark spot were observed throughout the test even when the driving time exceeded 100 hours: The life expectancy was very long (10 to 44 hours) even when set to an initial brightness of 3,600 cd/m² and driven at 85° C. with a constant current. Although, when tested similarly as above, the organic EL devices in this Example and the control organic EL device marked an approximately the same life expectancy at ambient temperature, the control organic EL device was obviously shorter in life expectancy (32 hours) at 85° C. than the organic EL devices in this Example using the coumarin derivative represented by Chemical Formula 18. With these results, the life expectancy for the organic EL devices of this Example was estimated to be 11,000 to 14,000 hours at a practical brightness of 300 cd/m², which would cause no obstructions in practical uses. The life expectancy for the organic EL devices of this Example using the compound represented by Chemical Formula 40 was estimated to be 13,000 hours at a brightness of 300 cd/m². Further the life expectancy for the control organic EL device was estimated to be 800 hours at a practical brightness of 300 cd/m² and 85° C., while the life expectancy for the organic EL devices using the coumarin derivative represented by Chemical Formula 18 was estimated to be 1,100 hours, which was significantly longer than that of the control, suggesting that the devices in this Example were large in durability against elevated temperature.

These results demonstrated that the organic EL devices of this invention was useful as green luminescent devices with a high color purity, as well as that one can realize the organic EL devices which are long in life expectancy and high in brightness and property even under severe conditions by using the coumarin derivatives of this invention.

EXAMPLE 9

Organic EL Device

A transparent substrate 1 which was prepared similarly as in Example 8 was transferred to the organic vaporizing room in the vacuum depositing apparatus which had been reduced to an inner pressure of 5×10⁻⁷ Torr, while the surface of ITO electrode as the cathode 2 was attached with an organic membrane-forming mask, after which the carbon crucible was heated to deposit the copper phthalocyanine represented by Chemical Formula 38 and TPTE in this order as the hole injection/transportation layer materials to give respective thickness of 10 and 30 nm, thus forming the hole injection/transportation layer 3. Subsequently; either coumarin derivative represented by Chemical Formula 18 or 20 as a luminescent layer material, obtained by the method of Example 1 or 6, and TPTE were simultaneously deposited in a weight ratio of 1:100 to form the luminescent layer 4, thickness of 20 nm, which was in contact with the hole injection/transportation layer 3, after which a phenanthroline compound represented by Chemical Formula 41 was deposited in vacuo to form the hole-blocking layer, thickness of 20 nm, while allowing it to contact with a adjacent membrane, as well as which tris(8-quinolinolate) aluminium was deposited to form the electron injection/transportation layer 5, thickness of 40 nm in this order.

Thereafter, the substrate 1 was transferred to the metal-depositing room in the vacuum depositing apparatus, deposited with lithium fluoride and aluminium in this order to give respective thicknesses of 0.5 and 150 nm to form the anode 6 which was in contact with the electron injection/transportation layer 5, after which the resultant device was sealed with a glass plate and ultraviolet-setting resin under nitrogen-aerating conditions, thus obtaining an organic EL device.

Separately, another organic EL device as control for comparison was prepared by using a quinuclidone compound in place of the coumarin derivatives of this invention. The results were as shown in Table 2.

TABLE 2 Wavelength of Luminescent layer luminescent Chromaticity material maximum (nm) diagram (x, y) A B C D E Remarks Chemical Formula 18 520 (0.34, 0.60) 1,157 4.7 10.5 2.2 — Present invention Chemical Formula 20 522 (0.34, 0.60) 1,160 4.8 10.5 2.3 — Present invention Chemical Formula 40 528 (0.27, 0.39) 121 0.5 1.1 0.021 — Control Note: The symbols “A”, “B”, “C”, “D”, and “E” mean “Luminescent brightness (cd/m²), “Power efficiency (lm/W)”, “Current efficiency (cd/A)”, “Life expectancy at ambient temperature (hour)”, and “Life expectancy at 85° C. (hour)”, respectively.

As seen from the results in Table 2, it was suggested that excited energy of TPTE was smoothly transferred to coumarin derivatives because the organic EL devices in this Example gave a luminescent maximum in the green region with a wavelength of around 520 nm, and non luminescence by TPTE observed: The organic EL devices in this Example were significantly narrow in half-band width for luminescence (85 nm), and good in color coordinates on the xy chromaticity diagram established by the CIE: The x and y value were 0.34 and 0.60 respectively. While, in the control organic EL device, as seen in the chromaticity diagram, the luminescence in a quinuclidone compound was admixed with the luminescence of TPTE, as the result, a low whitish green luminescence was given. These showed that excited energy of TPTE could not smoothly transferred to the quinuclidone compound.

As seen in Table 2, the organic EL devices in this Example gave at ambient temperature a luminescent brightness exceeding 1,100 cd/m², a good power and current efficiencies about 5 lm/W and 11 cd/A respectively when driven with a constant current of 11 mA/cm². While, the control organic EL device gave a low luminescent brightness of 121 cd/m² which was about tithe of that in the organic EL devices of this Example, as the result, a power and current efficiencies in the control were low (0.5 lm/W and 1.1 cd/A, respectively).

As to life expectancy, the organic EL devices in this Example gave prolonged expectancy exceeding 2 hours when set to an initial brightness of 2,400 cd/m² and driven at ambient temperature with a constant current: Non-luminescent parts such as dark spot were observed even when one subsequently allows them to release a luminescence during several times. While, the control organic EL device was significantly short life expectancy (0.02 hours) when tested similarly as above.

These facts demonstrate that luminescent agents in organic EL devices of this invention are useful for green color luminescent devices using TPTE as a host luminescent agent, as well as that one can realize the organic EL devices which are long in life expectancy, and high in brightness and property even under severe conditions by using the coumarin derivatives of this invention in combination with an appropriate host compound, regardless of carrier transportation properties of host compounds.

EXAMPLE 10

Display Panel

FIG. 2 is a brief figure of a single matrix type display panel (20 stripes of electrodes in the horizontal direction and 30 stripes of electrodes in the vertical direction) which comprises the organic EL device of this invention as substantial element: Such display panel can be prepared as follows.

The anode 14 of transparent ITO electrode is formed on one side of the glass substrate 10 in accordance with the method in Example 8, and then striped by the wet-etching method. The hole injection/transportation layer 16 and luminescent layer 18 are formed in this order in accordance with the method in Example 8, and the cathode 20 is striped with a mechanical mask, followed by sealing the organic EL device with a glass plate (not given in the Figure) and ultraviolet-setting resin. In the display panel of this Example, heat radiating means such as heat radiating plate and cooling fan may be provided on the backside of the cathode 20.

EXAMPLE 11

Information Displaying Equipment

FIG. 3 is a block diagram of an information displaying equipment which uses a display panel prepared by the method in Example 10. In FIG. 3, the reference numeral 30 represents a dc source, output voltage of 4.5 V, and its output terminals are connected with a pair of voltage-elevating circuits 32 and 34. The voltage-elevating circuit 32 is to supply a dc voltage of 5 to 12 V, and its output terminals are connected with the driving circuit 36. The other voltage-elevating circuit 34 is to supply a constant voltage of 5 V to the microcomputer 38.

The microcomputer 38 comprises the I/O interface 38 a for exchanging signals with external sites, the ROM 38 b for recording computer programs, the RAM 38 c for recording data, and the CPU 38 d for carrying out a variety of operations. To the microcomputer 38 is connected the clock pulse-generating circuit 40 for supplying 8 MHz clock signal and the oscillating circuits 42 and 44 which are to supply 5 to 50 Hz signal to control the displaying speed and 0.2 to 2 kHz signal to control the scanning frequency respectively.

The reference numeral 48 represents a display panel comprising the organic EL device of this invention as substantial element, which is connected with the microcomputer 38 through the driving circuits 36 and 46. The driving circuit 36 is to regulate the energization of dc voltage from the voltage-elevating circuit 32 to the display panel 48, which comprises a plurality of transistors connected with either stripe of electrode in the vertical direction in the display panel 48. Thus, when either transistor in the driving circuit 36 is turned on, the stripes of electrode in the vertical direction connected with the transistor is energized with the voltage from the voltage-elevating circuit 32. While the driving circuit 46 comprises a plurality of transistors connected with either stripe of electrode in the horizontal direction in the display panel 48, and when either transistor in the driving circuit 46 is turned on, the stripe of electrode in the horizontal direction connected with the transistor is grounded.

Since the information displaying equipment in this Example is assembled in this way, when one transistor in the driving circuits 36 and another transistor in the driving circuit 46 are turned on in accordance with the instruction of the microcomputer 38, a prescribed voltage is energized between corresponding stripes of electrodes in both vertical and horizontal directions in the display panel 48 to allow the organic EL device at the intersection to release a luminescence. Because of this, for example, when one stripe of electrode in the horizontal direction is chosen by appropriately controlling the driving circuit 36, the transistors connected with respective stripes of electrode in the vertical direction are sequentially turned on while grounding the former stripe of electrode: Thus, the chosen stripe of electrode in the horizontal direction is wholly scanned to display a prescribed picture element. A whole picture can be displayed by sequentially repeating such scanning in the vertical direction. Since the driving circuit 36 in this Example has a resistor which can supply a data enough to operate one stripe of electrode, it is desirable to drive transistors with the data recorded therein.

The information to be displayed is externally supplied in accordance with displaying rate and frequency, and alternatively supplied with data from the ROM 38 b where informations with prescribed patterns such as those in words has been recorded in the ROM 38 b. In case of displaying television broadcast in the usual NTSC mode, the received signals are separated into horizontal and vertical synchronizing signals in correspondence with the horizontal and vertical frequencies according to the broadcasting standard, and the image signals are converted into digital signals which meet to the pixel number in the display panel 48. Television broadcasts can be displayed on the display panel 48 by supplying these signals to the microcomputer 38 while appropriately synchronizing the signals.

INDUSTRIAL APPLICABILITY

As explained heretofore, this invention is based on the creation of a novel coumarin derivative, as well as on the discovery of its properties useful in industries. The coumarin derivatives according to this invention are very useful as luminescent agent in organic EL devices because the coumarin derivatives give a maximum for luminescence, a visible emission when excited, and a stable thin membrane in a glass state, as well as because exhibit a high thermal resistance. The coumarin derivatives according to this invention are also very useful as chromaticity adjusting materials for luminescent in organic EL devices because the coumarin derivatives give a maximum for luminescence in the visible region, and also large in a molecular absorption coefficient. Furthermore, it is possible that luminescent brightness in the organic EL devices is elevated by making more larger ratio of admixing with the coumarin derivatives and host compounds in the luminescent layer of the organic EL devices, and that, in some cases, an effective luminescent layer is consisted of only the coumarin derivatives according to this invention because the coumarin derivatives used in this invention are less liable to “concentration quenching” for luminescence than the conventional analogous compounds in comparison, as the result, there is the merit that one can decrease material numbers of consisting of the devices, and steps of forming the devices by omitting guest compounds which are essential elements in the organic EL devices. The organic EL device using such coumarin derivative according to this invention is advantageously usable in illuminants in general and also in a variety of information displaying equipments to visualize informations, for example, those in images and words because it is superior in luminescent efficiency and durability.

This invention with such outstanding effects is a significant invention which greatly contributes to this art. 

1. An organic electroluminescent device which comprises a coumarin derivative represented by either General Formula 1 or 2 and optionally a luminescent compound as a host compound, with the proviso that, when said luminescent compound is used, said coumarin derivative is used as a guest compound for said luminescent compound:

wherein in General Formulae 1 and 2, X denotes a carbon atom or a heteroatom; R₁ to R₁₄ independently denote a hydrogen atom or a substituent, provided that R₆ is not a cyano group R₃ and/or R₄ are absent when R₁ and/or R₂ form a ring structure containing both the nitrogen atom linked with R₁ and/or R₂ and the carbon atom linked with R³ or R⁴; at least one of R₉ to R₁₂ is a hydrocarbon group which may bear a substituent; R₁₃ and R₁₄ do not form a phenyl group and in the case that X is a divalent or trivalent heteroatom, R₇ and/or R₈ are absent.
 2. The organic electroluminescent device of claim 1, wherein said coumarin derivative is represented by either General Formula 3 or 4:

wherein in General Formulae 3 and 4, X denotes a carbon atom or a heteroatom; R₅ to R₁₄ independently denote a hydrogen atom or a substituent, provided that R₆ is not a cyano group; at least one of R₉ to R₁₂ is a hydrocarbon group which may bear a substituent; R₁₃ and R₁₄ do not form a phenyl group in the case that X is a divalent or trivalent heteroatom, R₇ and/or R₈ are absent; and R₁₅ to R₁₈ independently denote hydrogen or a substituent.
 3. The organic electroluminescent device of claim 1 or 2, which comprises a luminescent layer material a coumarin derivative represented by any one of General Formulae 1 to
 4. 4. A display panel comprising the organic electroluminescent device of any one of claims 1 to
 3. 5. An information displaying equipment comprising the organic electroluminescent device of any one of claims 1 to
 3. 6. A luminescent agent in an organic electroluminescent device comprising the coumarin derivative represented by either General Formula 1 or 2:

wherein in General Formulae 1 and 2, X denotes a carbon atom or a heteroatom; R₁ to R₁₄ independently denote hydrogen atom or a substituent, provided that R₃ and/or R₄ are apparently absent when R₁ and/or R₂ form a ring structure containing both the nitrogen atom linked with R₁ and/or R₂ and the carbon atom linked with R₃ or R₄; at least one of R₉ to R₁₂ is a hydrocarbon group which may bear a substituent; and in the case that X is a divalent or trivalent heteroatom, R₇ and/or R₈ are absent.
 7. The luminescent agent in the organic electroluminescent device of claim 6, wherein said coumarin derivative is represented by either General Formula 3 or 4:

wherein in General Formulae 3 and 4, X denotes carbon atom or a heteroatom similarly as in General Formula 1 or 2; R₅ to R₁₄ independently denote hydrogen atom or a substituent, provided that R₆ is not a cyano group; at least one of R₉ to R₁₂ is a hydrocarbon group which may bear a substituent; R₁₃ and R₁₄ do not form a phenyl group in the case that X is a divalent or trivalent heteroatom, R₇ and/or R₈ are absent; and R₁₅ to R₁₈ independently denote hydrogen or a substituent. 